Numerous studies have shown that co-adsorbates and solvents influence the selectivity and rate of heterogeneous catalytic reactions. Fundamental understanding of how protic and aprotic polar co-adsorbates affect different bond cleavages will give us valuable insight into how co-adsorbates affect the reaction mechanism, rate and selectivity of catalytic reactions. Here we present a density functional theory (DFT) calculation of how protic (water and methanol) and aprotic (dimethyl sulfoxide, acetonitrile and acetone) polar co-adsorbates affect the C-OH and O-H bond cleavage of acetic acid intermediates during acetic acid decomposition over Pd (111). Our results suggest that co-adsorbed water and methanol favors O-H bond cleavage over C-OH bond cleavage. While co-adsorbed acetonitrile enhances C-OH bond cleavage and inhibits O-H bond cleavage, but dimethyl sulfoxide enhances both C-OH and O-H bond cleavages. These calculations give insights into how different co-adsorbates affect bond cleavages differently, which can lead to changes in selectivity and reaction rate.

Effects of aprotic and protic polar co-adsorbates on C-OH and O-H bond cleavages

ACS Fall 2021

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